Fibrous roll impregnated with developer liquid and method of making same

ABSTRACT

A roll and method of making same which is impregnated with a large amount of a developer liquid while substantially excluding ambient air. The pressure of rolling causes the liquid to ooze out of the peripherial surface of the roll in small fixed quantities and to be transferred to sheet material such as paper rolled therewith. Such a roll is capable of copying for an extended period of time without replacement and without necessity of replenishment of the developed liquid.

United States Patent 1 1 r i v 1111 3,814,054

Tajihi i 1451 June 4, 1974 [54] 1113110115 ROLL mpmzcu rE wrm, 2,358,851 9/1944 Chollar 101/34s-x DEVELOPER LIQUID 'AND METHOD OF 2,530,388 1 H1950 Gullixson... l 18/258 X 2,801,461 8/1957 Kusters 29/l48.4 D MAKmG SAME 3,159,144 12/1964 Duncan et a1. 222/187 x Q1 A [75] Inventor: Michio Tajihi, Osaka, Japan 3,336,866 8/1967 Hawthorne 29/125 X 1 3,443,300 5 1969 L' k' 29 125 1 Asslgfleei Kabushlkl Kalsha Yamamoto 3,710,469 1/1973 29/125 Kogyosho, agoya C ty, apa 3,711,913 1/1973 Galeone 29/125 x Filed: Oct 19 1972 3,724,047 4/1973 Peterson .1 29/132 X PP 300,777 Primary Examiner-Charles W. Lanham Assistant Examiner- D. C. Reiley, Ill

[30] Foreign Application Priority Data Attorney, Agent, or FirmFrank J. Jordan Aug. 29. 1972 ,Japan... 47-85852 v 1 [57] ABSTRACT [52] US. Cl 118/258, 29/124, 29/125,

7 29 130 29 132 29/1484 D, 101/348, A roll and method of making same which is impreg- IQ1/367, 222/187 nated with a large amount of a developer liquid while 51- Int. Cl B67d 3/00, BOSc 1/06 Substantially excluding m i The P 9 9 53 Field f Seal-chm 29 D, 419 120, 121 R1 roliing causes the liquid to ooze out of the peripherial 29/124 125 0 3 264/257, surface of the roll in small fixed quantities and to be 101 34 3 7; 22 7; 18/258 transferred to sheet material such as paper rolled therewith. Such a roll is capable of copying for an ex- [56] 1 References Citd h tended period of time without replacement and with- UNITED STATES L S out necessity of replenishment of the developed liquid.

1,284,443 1 H1918 Plant... 101/348 X 5 Claims, 3 Drawing Figures 1 FIBROUS ROLL IMPREGNATED WITH DEVELOPER LIQUID AND METHOD OF MAKING SAME The present invention relates to a fibrous rollimpregnated with liquid'which is to be exuded in fixed and small quantities and a manufacturing method therefor.

Such a roll is preferably used as a roller capable of holding a considerably large amount of liquid therein while substantially excluding ambient air and of trans-' The diazotype methods have the advantages of avery susceptible coupling reaction, a stable reacted azo color, sharp image contrast, and image dissolving power second onlytosilversalts. v

However, the diazotype methods dohave serious disadvantages. In the one-component diazotype method wherein the photosensitive material carried by a paper sheet is a diazonium compound which must be developed with a coupler, it is necessary to apply an excessive amountof developer liquid so that the copy papers remainsomewhat wet even if a subsequent drying treatment'is provided. Whereas the theoretically required amount of the usual developing agent is from 3.0 to 5.0 gr. per l m it isdifficult to apply such small amount of the developing agent which is generally provided in the form of the aqueous solution. so as to facilitate homogeneous development. Various unsuccessful proposals have been made forapplying small amounts of the developer liquid. Furthermore the developer liquid generallyhas a pH value rangingfrom 1 l to 12 so as to be hazardous. All of the proposals have required that the hazardous developer liquid be supplied to the applicator which inevitably jeopardizes human safety. In the two-component method wherein the sheet paper careven more difficult.'Furthermore monoethanolamine is ries a diazonium compound-and a coupling component which are not reacted under ordinary conditions but reacted at a suitable pH conditions to form the azo dye, ammonia is used for increasing the pH value. Whereas the so-called dry method was used for a long time in the photocopying field, the strong and offensive odor of the ammonia fumes together with the threat to human healthhas causedthe dry method to be replaced by newly developed copying methods. However, a new developing agent for the two-component diazotype method has been recently proposed to replace ammonia so that thedry method may be re-evaluated. For instance according to British Patent No. 816,601 some aliphatic amines, among which ethanolamines are preferable. Monoethanolamine is probably most preferable. This sort of developing agent effective in the amount ranging from 1.0 to, 3.0 gr; 1 m is to be used also in the form o'fan aqueous solution; thus encountering the same problems as the one-component method referred to above. Applying the developing agent as a homogeneous solution in such small amounts would be readily oxidized by the ambient atmosphere.

Various rollers or roll applicators have been proposed but have been found to be unsatifactory since they can not apply the liquid in homogeneous form and in'the controlled small quantities.

Applicant has previously proposed a fibrous roll for applying monoethanolamine developer liquid in Japanese Patent Application No. 64 930/65 of October 22,

, 1965 which was opened for public inspection on March 8, 1972 under the number of 8 1 16/72. This applicator roll is manufactured by blending hygroscopic fiber material such as cotton which has been impregnated with a developer liquid comprising monoethanolamine and gasifying agent such as camphor, with nonhygroscopic fiber material such as synthetic fiber, and with mineral fiber which is capable of allowing gasified developing agent to permeate and diffuse therethrough. The

.blended fiber material is pressed together to form a roll, which is mounted on a hollow tube which extends centrally and axially therethrough. The central tube contains a heater means and is surrounded by a plurality of hollow tubes which extend axially and are parallel with each other. Each of the surrounding tubes has perforations formed in its peripheral wall for feeding the developer liquid;

However, blending treatment for attaining homogeneous distribution of two or more sorts of fibers having different characteristics is difficult. The developed liquid must still be used in excessive amounts in order to ensure even application. The poor liquid holding ability of the roll requires that the liquid continuously supplied to the ,roll applicator through said surrounding tubes.

A copier machine equipped with such a roll application should be provided with a reservoir to which the developer liquid must be occas'sionally added. The roll previously proposed by applicant fails to avoid or to overcome completely the faults referred to above.

One object of the instant invention is to provide a roll impregnated with the developer liquid which may be used as an applicator roller in the diazotype copier machine whereby the faults referred to above are completely avoided and overcome. A

Another object of the invention is to provide a roll capable of holding a considerably greater amount of the developer liquid so that many more copying operations can be made from a single roll without'requiring replenishment of the developer liquid.

Another object is to provide a roll capable of exuding the developer liquid impregnated therein in controlled and very small quantities at the peripheral surface of the roll.

Still another object is to provide a roll capable of sub- The still further object is to provide a roll suitable for very compact and cheap diazotype copier machines.v

Other objects and advantages will become apparent to thosed skilled in the art upon a reading of the description. The disclosed roll maybe used for various purposes other than for dispensing and applying the developer liquid. t

The above objects may be attained by forming into sheet form purified cellulose fiber material having fiber length longer than a few millimeters and of area] weight ranging from 400 to 500 gr/m A disk having a central hole is stamped out of the sheet. A plurality of such disks are saturatedly impregnated with the desired liquid. The impregnated disks are then collected and secured together by inserting a shaft into the disk central hole to form a'cylindrical body. The cylindrical body is pressed in the axial direction to allow some of the impregnated' liquid to be squeezed out so that the total amorphous'material, the swelling becomes so great that not onlysaid amorphous material but also saidlow polymerizationmaterial is exuded out. On the other hand, gelation can occur in low purity fibers in the limited swelling condition, depending on the nature of the im-- pregnating liquid. Accordingly the cellulose fiber mate rial must be of high purity so that a-cellulose content is increased up to.e.g. 98 or 99 percent and alkali soluble contentor alkali solubility is decreased down to e.g.

2 percent whereby the fiber material may hold the liquid in the limited swelling condition. A sheet is formed from such fiber, preferably from cotton linter pulp so as to-be of areal weight in the order of from 400 to 500 gr/m and of fiber length longer than a few millimeters. The fiber length is not critical but'the preferred range is from 3mm to 18 mm. The thickness of the sheet is also. not critical but preferably ranges from 1 mm to 3 mm. No sizing agent should be used.

A plurality of disks stamped out from the sheet are saturatedly impregnated with the concerned liquid, for example, an aqueous solution of monoethanolamine having the usual additives for developing the twocomponent diazotype material. The amount of the liquid required for saturation impregnation naturally depends on the nature of the liquid, but the amount of the preferred liquid --required is almost-3 times the total weight of the dry disks. In other words the cylindrical body consisting of many disks impregnated with the liquid weighs about four times as much as the total weight of the disks before the impregnation.

If the cylindrical body is pressed in the axial direction to allow some of the impregnated liquid to be squeezed out so that the weight thereof is two to three times that of the dry disks, very compact roll can be obtained. The shore hardness thereof is about to 55 so that abrading or grinding of the peripheral surface of the roll is possible despite the fact that the roll consists solely of cellulose fiber. If necessary for facilitating the abrading or grinding operation, a very small amount of melamine resin .may be added when the sheet is formed. It has been found that the pressure depends upon the hardness, which i'nturn depends upon the exudation rate. Thus, the desired material for the roll is produced by controlling the exudation rate. The peripheral surface of the roll is slightly damp which can be barely detected by touching. Because of even density distribution in the roll, the dampness is even over ing drawings, in which;

the entire surface of the roll and immediately following oozing out the liquid is transferred to any other material such as a sheet paper contacted therewith.

When the roll surface is properly ground or abraded, it is possible to apply the exudated liquid evenly to the material to be treated, but the preferred embodiment is to'cover the roll with a fabric woven or knitted from nonhygroscopic yarn such as synthetic resin fiber or mineral fiber in order to ensure more even liquid application.

The invention is explained in greater detail and some examples are given in connection with the accompany- FIG. 1 shows a pluralityof fibrous disks, each havinga central hole, positioned in alignment and being dipped in a'liquid contained in a vessel,

FIG. 2 shows a cylindrical body formed by assembling and securing a plurality of the liquid impregnated disks together by inserting a shaft through the. holes of the disks, and show a press machine for pressing said cylindrical body axially to form a compact roll, and

FIG. 3 is a perspective view of the manufactured roll partly cut away for showing the inner construction.

EXAMPLE 1 From cotton linter pulp 'of acellulose content 98.80 percent, alkali solubility 2.00percent, alcohol-benzene extract 0.09 percent, ash content 0.07 percent, viscocity (TAPPI STANDARD T-230 CED) 37.5 cp a sheet was formed with Canadianfreeness of 51.0 cc.-so

as to be of thickness l mm, areal weight 500 gr/m,

density 500 mgr/ch1 moisture content lower than 10 percent. As seen in FIG. 1, the sheet was stamped out of a disk 1 having adiameter of about 7.0 cm and having a central hole 2. A plurality of such disks 1 were dipped in a developer liquid 3 contained in a vessel 4. The developer liquid for the two-component diazotype material has the following composition:

Monoethanolamine 20.0 gr. Triethanolamine 10.0 gr. Ethylcneglycol I00 gr. Nonionic surfactant 0.5 gr. Sufficient water to make the total I cc.

About 1,253 vgrjliquid was impregnated in the disks which weighed 445 gr. before 'the impregnation, thus the impregnated liquid amount is about 2.8 times the total weight of the dry disks.

As shownin FIG. 2, a plurality of disks 1 were assembled and secured together by inserting the shaft 5 through the central holes 2 of the disk to form a cylindrical body. On each of the opposite ends of said cylindrical body was respectively mounted a metal disk 6 whichwas in turn held by a flange washer 7 -screwed on the shaft 5. This assembly was subjected to pressing by a pneumatic press machine having a base stand 8 and a post 9 vertically standing up therefrom. Said post 9 has a pneumatic press cylinder 10 at the upper end thereof. The cylinder 10 has two conduits 11 and 12 for letting air under pressure in and out to actuate a piston 13 for vertical movement so that a press frame 14 mounted at the free endof said piston- 13 is movable toward or away from said base stand 8. Said fibrous disks assembly was placed in the vertical position between said base stand 8 and said movable press frame 14. Under controlled operation, the frame 14 was lowered .to press the upper metal disk 6 down and conse-'- quently press the fibrous cylindrical body in the axial ill , had an exudation rate of 3.0 to 5.0

direction so that the total weight of the fibrous disks and the impregnated liquid was reduced to 890 gr. which is about 2.0. times the total weight of the dry disks. Thus about 445 gr. liquid remained impregnated. The 445 gr. is equal to the total weight of the dry disks. The resulting roll was very compact and showed Shore hardness of 55. This compact roll was subjected to a grinding step I for finishing the peripheral surface thereof so that it is smooth and a substantially geometrically true cylindrical body is formed.

FIG. 3 shows a finished peripheral surface so smooth and individual disks constituting the roll can not be distinguished at a glance of the surface. The. finished roll was covered over the whole peripheralsurface thereof with a fabric 16 knitted from nylon yarn of 90 denieraccording to the circular knitting method in the stocking manufacture so as to be about 25 percent stretchability, 50 mesh.

When the disclosed roll was used as a rotary driven applicator, actual and successive developing operations were carried on employing the usual commercial twocomponent diazotype photosensitive paper sheets. Each of the photosensitive papers was exposed to light to form the latent image of the original and was contacted by the rotating applicator roller whereby the developer liquid oozing out of the roll at the peripheral surface was absorbed. After 20 seconds reaction time, copy-images were developed, each having very sharp contrast and high resolution. Successive development operation of 10,000 sheets of diazopapers produced the same result. The experiment was conducted by using the same roll to develop 100 sheets every morning and every afternoon for over 50 days. The roll was weighed every day after completion of developing 200 sheets in order to determine how much of the developer liquid was consumed. Although some fluctuations possibly depending on the 'weather conditions such as humidity and temperature was observed, the average exudation rate .of the developing agent was determined to be in the range of L5 to 2.5 gr/m In order to apply the smallest sufficient amount of the developer liquid, dry copy paper having less than ten percent moisture was employed. a

IEXAMPLEZ to be impregnated within the roll had the following compositions:

Hydrochlorate of 3-hydroxy-2-napthoic acid ethunolamide Potassium phosphate Thioureu Triethanol Nonionic surfactant.

Sufficient water to make the total The resulting roll possessed a Shore hardness of 50 and v gr/m which was suitable for the developing agent.

The roll impregnated with such developer liquid was similarly subjectedto the actual development experiments and siinilar' results were obtained.

EXAMPLE3 A roll manufactured according to the disclosed method was used as an applicator roller for the twocomponent diazotype method. Here what is applied to the photosensitive paper is not the alkaline liquid but an aqueous solution of an ammonium salt which is thermally decomposed to generate hydrated ammonia gas.

The roll was manufactured as set forth in Example 1 except that the sheet had a thickness of 3 mm and density of 40 mgr/m The liquid to be impregnated had the following composition:

Ammonium carbonate 3 Lauryl ether 3.0 gr. Nonionic surfactant 0.5 gr. 0 cc.

Sufficient water to make the total 10 wherein the diazo-paper was contacted with the rotat ing roller to absorb the exuded liquid and was then heated to a temperature of 120C. The obtained copy was similarly satisfactory. A slight odor of ammonia was detected but disappearedwithin about one minute. The odor disappeared because the copy paper cools upon leaving the heater means and thus ammonia is reduced to ammonium carbonate.

It was surprising found that when the cylindrical body consisting of a plurality of fibrous disks saturatedly impregnated with the concerned liquid is axially pressed under a controlled force, a compact roll of unexpectedly great hardness can be obtained, and that the hardness can be controlled at will by varying the exudation rate. The instant invention is useful not only in the copying technique field but also in various fields in which a roll impregnated with a large amount of liquid which is to be exudated-at the peripheral surface evenly and in small quantities so as to be applied little by little to any material contacted by the roll. Theinvention has been actually applied to the two-component diazotype copier machine. When two thirds to three fourths of the impregnated developer liquid has been consumed. the roll is preferably replaced with a fresh one so as to ensure satisfactory copying. A single roll may last one year or more when used in home copying or small-scale business copying. There is substantially no danger of the monoethanolamine developer agent being oxidized since it is confined within a very compact roll structure without effective access to ambient air. Thus the diazotype copier machine is not detrimental to human health.

What is claimed is;

1. Method for manufacturing a fibrous roll impregnated with a developer for diazotype photosensitizing sheet paper to be exuded in fixed and small quantities comprising the steps of forming purified cellulose fiber having a oi-cellulose content of more than 98 percent and alkali solubility of less than 2 percent in a sheet of fiber having a length longer than a few millimeters and of areal weight ranging from 400 to 500 gr/m, stamping out a disk having a central hole from said sheet,

saturatedly impregnating a plurality of said disks with the developer, collecting said liquid impregnated disks together in aligned array, inserting a shaft into the central aligned holes to form a substantially cylindrical body, forming a compact roll by pressing said cylindrical body in the axial direction to allow some of the impregnated liquid to be squeezed out so that the total weight of the cylindrical body is 2 to 3 times that of the dry disks before the liquid impregnation, and abrading the peripheral surface of said roll.

2. Method as claimed in claim 1, which comprises a further step of covering the resulting roll with a rough mesh fabric made from nonhygroscopic nature fiber.

3. Method as claimed in claim 1, in which cotton linter pulp is used as said purified cellulose fiber material.

4. Method as claimed in claim 1, in which said pressing is made in such an extent that the resulting compact roll is of Shore hardness ranging from 40 to 55.

5. A fibrous roller for use as an applicator roller for applying liquid at the peripheral surface thereof to a sheet material to be contacted therewith, comprising a plurality of disks arranged in juxtaposed array to form a cylinder body, each of said disks being made of purified cellulose fiber having a a-cellulose content of more than 98 percent and alkali solubility of less than 2 percent, each of said'sheets initially being in the form of a sheet having an areal weight ranging from 400 to 500 gr/m each of said disks being impregnated with a developer for diazotype photosensitizing sheet paper, said cylindrical body having a total weight within 2 to 3 times that of the dry weight of said disks before impregnation of the latter, said cylindrical body having an abraded peripheral surface. 

2. Method as claimed in claim 1, which comprises a further step of covering the resulting roll with a rough mesh fabric made from nonhygroscopic nature fiber.
 3. Method as claimed in claim 1, in which cotton linter pulp is used as said purified cellulose fiber material.
 4. Method as claimed in claim 1, in which said pressing is made in such an extent that the resulting compact roll is of Shore hardness ranging from 40* to 55*.
 5. A fibrous roller for use as an applicator roller for applying liquid at the peripheral surface thereof to a sheet material to be contacted therewith, comprising a plurality of disks arranged in juxtaposed array to form a cylinder body, each of said disks being made of purified cellulose fiber having a Alpha -cellulose content of more than 98 percent and alkali solubility of less than 2 percent, each of said sheets initially being in the form of a sheet having an areal weight ranging from 400 to 500 gr/m2, each of said disks being impregnated with a developer for diazotype photosensitizing sheet paper, said cylindrical body having a total weight within 2 to 3 times that of the dry weight of said disks before impregnation of the latter, said cylindrical body having an abraded peripheral surface. 